Manufacture of liquid hydrocarbons suitable for motor fuel



Dee. 17, 1946.

MANUFACTURE J. R. RosE 2,412,837

OFy LIQUID HYDROCARBONS SUITABLE FOR MOTOR FUEL Filed June 26, V1945l INVENTOR.

I BY @wir HTroENEY aou/o Hmmm Patented Dec. 17, 1946 y MANUFACTURE OF LIQUID HYDROCABBON S SUITABLE FOR MOTOR. FUELA James R. Rose, Arlington, Va., assignor,A by direct f v and mesne assignments, to Potomac Hydrocarbon Process Corporation,

corporationof Delaware p ashington, DLC., a

Application .lune 26, 1945, Serial No. .601,675

,4 claims. (c1. 19t-52) This invention relates to the manufacture of liquid hydrocarbons suitable for motor fuel, and more particularly to the manufacture of highoctane gasolene.

' The general purpose 4and object of the invention Describing the apparatus or system shown in` the aforesaid drawing, I0 denotes a pump having an `inlet II for liquid hydrocarbon and an outlet` I2 communicating by a pipe I3 and through a valve I4 with a cooler I5, the lower portion of which in turn is connected by a pipe I6 with a col-4 lector Il provided with a valved outlet pipe I8 extending from the upper portion thereof. l

A valved pipe I9 communicates at one end with the lower portion of the collector and at its opposite end with the first cracking element20 in the bottom row of several vertically spaced rows of such elements, the said elements being shown as of the usual tubular form and the tubes in different rows being connected in series and the final tube in each row being connected with the first receiving tube in the row next thereabove. Four such rows are shown, the same being arranged within a cracking stove, and the nal tube in the uppermost row communicates by means of a pipe 2`| with a catalyte container tube 22' which is shown as, extending horizontally of the stove and as located adjacent to the top and preferably about midway between the sides of the stove.

The container tube 22 communicates through a pipe 23 with the lower portion of a large vertically arranged catalyte container tube 24 located within the stack 25. A pipe 26 communicates at one end with the upper portion of this catalyte container tube `and at its other end with Va cooler 28, `the pipe being provided with an expansion Avalve 2l intermediate of the container tube 24 and the said cooler 28. From the cooler 28, a pipe 28a extends to the top of a collector 29; a valved pipe 30 communicates at itslower end with the lower portion of the collector 29 and at its upper portion with a stabilizing tower 3 I, preff erably substantially midway `of the height of the latter.` This toweris packed with suitable relll fractory` material, such as` Berl saddlesfl or Raschig rings. A steam coil 32 is located at the lower portion of the tower and a water circulating coil 33 Within the upper portion of the tower.` A valved pipe 34 communicates at one end withthe lower portion ofthe tower and atits other end with a tank 35 in which the finished product is collected.

A valved pipe 36 extends from the top of the tower -to the top of a compressor 3l; and a valved pipe 38 extends from said compressor to the cooler I5, conveniently through a portion of `the pipe I3. y

In operating the apparatus or system just described, a liquid hydrocarbon base element, such as crude oil "and/or low octane gasolene, is in-L trocluced into the pump I0, where it is subjected to a pressure of from 700 lbs. to 1000 lbs. per square inch, the pressure varying in accordance with the nature of the particular liquid hydro` carbon used, but not being below 700 lbs. per square inch. From the pump, the liquid is delivered through the valved pipe I 3 into the cooler i5 and thence into the liquid collector I1.

From the collector Il, the liquid flows, under the pressure `imparted thereto by the pump, through the cracking tubes 20 in succession and thence into one end of the catalyte container tube 22 which preferably contains a catalyte composed of a mixture of carnotite and barium uoride,

preferably in the proportions of 16 parts by weight of carnotite to from l to 12 parts by weight of barium fluoride (as set forth in my Patent 2,126,284). The gaseous product resulting from the foregoing cracking operation passes from the opposite end of the tube 22 into the bottom of the vertical catalyte container tube 24. The catalyte which I `use in this container tube is preferably that described and claimed in my Patent 2,173,376,`

issued September 19, 1939, and consisting of the following ingredients mingled in substantially the following range of proportions:

Carnotite 25% to 100% by weight of the total weight of all other ingredients.

The container tube 24, it will be noted, is ar-` ranged within the lower portion of the stack which receives the products of combustion from the'crackingistove whereby -the said container Parts by weight` uct resulting from the passage of the hydrocarbon through the cracker tubes and the catalyte container tubes is delivered to a pipe 2S, provided with an expansion valve 21 where by the pressure on the gaseous product'is quickly 'reduced to 150 lbs. per square inch, thereby setting .up an intense cooling action, with resultant liquefaction, the liquefaction being facilitated by the cooler 28. livered through a pipe 28a to the collection chamclaim is:

ber 29; and from the collection chamber the liquid is delivered through the pipe 30 into the stabilizing tower, midway of the height of the latter, where it is diffused over the refractory material, being subjected to the heat of the steam coil32'in the'bottom of the tower, which serves to boil off the lighter gases and leave behind the heavier polymers, which .are largely within the gasolene range of hydrocarbons.

The gases in the upper portion of thev tower are subjected to the action of the coil 33 which serves `to condense the heavier of the gases which reach this point, the condensate-thus formed consisting ofthe heavier polymers which are largely within the gasolene range of hydrocarbons and which are collected in the bottom of the. tower, whence Vall such..polymers are delivered to the tank .35.' VThe lighter gases, which consist of a mixture. of hydrocarbons of the CH4, C21-Ie, Cal-Is and 04H10 series, are conducted by the pipe 30 to the compressor 31 where they are subjectedto the same pressure as that imparted to the hydrocarbon'liquid by the. pump I0. The components that are condensable into liquid at this pressure are removed from the mixtureA while theuncondensable components may be delivered as dry gas iroma collector l l through the pipe i8 `and may then be used as lfuel for a burner A which serves to heat the tubes in the cracking stove and the tube24`in the stack 25. `The operation of the system or apparatus withthe base, hydrocarbon constituted by the mixture of the normally. liquid hydrocarbon with that obtainedby compressing the gaseous product from the stabilizer tower will proceed from this point in the manner described hereinbefore in connection with the liquid hydrocarbon from the pump I0.

Asthe Vflow, of cracked material in a gaseous form is always toward a zone of less pressure, I have taken advantage of this fact to cause the mixture of liquid hydrocarbon delivered by the pump I with that resulting from the condensation of gases supplied to'and delivered from the compressor 31 to move constantly upwardly from the time Vthe mixture' enters the rst` row of cracking .tubes until it reaches the expansion chamber 28.. Furthermore, the crude oil is introduced to the hottest cracking element or horizontal rows of cracking tubes, following which the streamows upwardly rthrough the cooler cracking tubes and toward the outlet. Due to this kmode of introducing and circulating the hy-.` drocarbons through' the cracking and catalyte tubes, the formation of; heavy bottoms is prevented to a large degree. It should be noted that the liquid hydrocarbon delivered by the pump lilA andfthat delivered from the compressor 31' are under apressure of from 700 to 1000 lbs.l per square inch and that the mixture of the hydrocarbons from these two sources is subjected tov this pressure until th gaseous productresulting Vfrom the cracking operationpassesithe expansion valve 21.

It will be noted further that the arrangement,

lyte container tube 24 in the stack enablesa most Y efficient utilization vof the heating agent 'for the `purpose *of cracking the hydrocarbon vmixture supplied thereto. v

' Having thus described my invention, whatI 1. An apparatus or system for the lpurpose specied comprising pressure-creating means, means for supplying a hydrocarbon base fluid to said pressure-creating means, a cooler, a conduit for delivering the fluid from the pressure-creating Ameans tothe cooler, Ia cracking stove, {c tplurality ,ofV communicating cracking elementsar-v rangedone above another in said stove and a catalyte container o greater diameter thanthe cracking elements and located above the `cracking elements in the said stove andy-communicate ing with. the uppermost of. said elementsa con.- duitior delivering uid from the cooler toithe lowermost oflthe said cracking' elements, a burnerin saidstove below the said` elementsfor. heating the saidelements .andthe catalyte con* tainer, a vertical stackextending above the stove and connected to the .stoveat a point-adjacent to the upper portion of the latter, means for de livering, thereinto the products of .combustion from the burner in said stove which. have contacted the said elements and thesaidcatalyte container,l ay vertically extending catalytev con-V tainer inthe said stackcommunicatingat apoint adjacent to its bottornwith the` `iirst mentioned catalyte container and arranged to be exposed. substantially throughout its entirelength to the rising products of co-mbustion in said stack, a

delivery pipe communicating with the upper por.r

Ymunicating at one end with thesaidfcollector andat its upper `end with said stabilizing tower substantially midway of the height ofthe'tower,

a heating device in the lowerportion-of said stabilizing tower, a condensingV device in the upper portion Vof said stabilizing tower, a' pipe comlmunicating with the tower below theheating device, and a tank withl which the deliveryend,

of said pipe communicates. l i

' 2. In the apparatus'or system as set-forth. in

claim 1, a compresso-r, means for delivering nonv condensed gases from the stabilizing tower, tothe said compressor, and means for/delivering the Huid from the said compressor into the conduit which deliversfluid into the 'lowermost ofthe.

cracking elements.

3. The process'of manufacturing liquid hydro,-4 carbon suitable for motor fuel which comprises.. subjecting a. hydrocarbon base fluid to a pressure of from 700 tolODO pounds per square inch; coolfvv ing the fluid and conducting the same under such pressure in' a constantly Vupward direction' through a vertically arranged series of cracking4 elements and a catalyte container; subjecting thesaid cracking elements and the c at'alyteV con-` tainerto a heating .medium contacting'iirst they lowerm'ost ofthe cracking elements "and thereafter contacting the cracking elements thereabove and the catalyte container whereby the said elements are subjected to an initial temperature, in the lowermost of said cracking elements, of from '700 to 1200o F.; delivering the gaseous 'product from the said catalyte container to a second catalyte container located above the rst catalyte container and heated by the heating medium which has rst contacted the cracking elements and the rst catalyte container; liquefying, by sudden reduction of pressure and by cooling, the gaseous product produced within and delivered from the second catalyte container; and subjecting the liquid thus obtained to agstabilizing action thereby to evolve, from such Iiud, hydrocarbon gases and heavy liquid hydrocarbon polymers.

4. In the process set forth in claim 3J delivering the hydrocarbon gases not condensed by the stabilizing action into the hydrocarbon base uid under a pressure of from 700 to 1000 pounds per square inch and together with said base uid into the vertically arranged series of cracking elements.

JAMES R. ROSE. 

